Process for condensation products of thiourea compounds



Patented Nov. 26, 1946 -UNITED STATES PATENT OFFICE PROCESS FORCONDENSA'I'ION PRODUCTS F THIOUREA COMPOUNDS No Drawing. Originalapplication January 19.

1939, Serial No. 251,850. plicstion July 14, 1943, Serial No. 484,732.

Divided and this an- Switzerland January 22,1938

Claims.

1 According to the present invention new condensation products areobtained by reacting a thioures compound containing the group KS-O witha member of the group consisting of methylol compounds oi amides, urea:and urethanes, each member containing at the most 13 carbon atoms atleast 7 of which being connected.

As thiourea compound containing the group may be used thiourea,N-methyi-, N:N'-dimethyh, N:N:N-trimethylthiourea. N-monoethylthiourea,N-phenylthiourea, N:N'-diethylthiourea, potassium,N-phenylthiourea-parasulfonate, N:N-diethyl-N-hydroxy-thioureamonothiobiuret (NH: CO NH CS N112) thio-aliophanic acid methyl esterorthe like.

Quite generally may be used .thiourea com pounds of the formula N-Ih HS-R (Cl. HM-5) are also designated as "pseudo-thioureasfi radical suchasis therefore designated in the present specification as "a. radical of apseudo-thiourea compound."

As carboxylic acid methylolamides there may be used, for instance, themethylolamides oi capyrlic, capric, lauric bcnzoic, toluic,parahexylbenzoic, hexahydrobenzoic acid. These N-methylolcarboxylic acidamides, insofar as they have not been described, are accessible withoutfurther information by processes analogous to those that are known.

As methylol compounds oi urethanes there may be used, for instance, theN-methyloi compounds obtainable from the urethanes corresponding withthe aliphatic alcohols having 3 to 13 carbon atoms by treatment withformaldehyde in the usual manner.

The ureamethylol compounds which may be used as parent materials mayalso be made by processes analogous to those known and without furtherinformation from the corresponding ureas, for example hexyloroctyl-urea.

The reaction between the cited formaldehyde derivatives and thethiourea. compounds containin an group may be effected by mixing thecomponents at room temperature or at a raised temperature, for example50 to 0., preferably in the presence of a solvent, for instance benzene,chloroform, carbon tetrachloride or glacial acetic acid. When a methyloicompound such as a. carboxylic scid-N-methylolamide is subjected to thereaction it is frequently advantageous to use a strong acid, forinstance hydrochloric acid, as a. condensing agent, if desired togetherwith a diluent.

According to the present process there are generally obtained salts ofproducts containing at least seven connected carbon atoms andcorresponding to the general formula wherein R stands for an organicradical free from water-solubilizing groups and containing at the most12 carbon atoms. X stands for a bridge in which the sum of the atomicweights of the atoms connecting CH: with R in a straight chain is 26,the straight chain containing the same atom at the most once, andwherein R1 stands for the radical of a pseudo-thiourea compound thesulfur atom of which is bound to the CHz-group, the latter being linkedto such an atom of the bridge X the atomic weight of which amounts to atleast 14, which salts are liquid to solid substances soluble in water toform solutions which are decomposed by boiling or when treated withalkaiies, water-insoluble compounds being formed. As salts there comeinto consideration particularly the salts formed with mineral acids,such as hydrohallc acids, for example hydrochloric acid, bydrobromicacid, sulfuric acid, further the salts formed with organic acids, suchas formic acid, or acetic acid. An example of such a salt is the productof the formula wherein the acid is bound by the pseudo-thiourea radical.

The condensation products obtainable by the invention are, in the formof the salts which they form with acids. soluble in water. The stabilityof the solutions thus obtained may be increased by the addition ofcertain auxiliary substances, for instance thioureas, ureas, capillarycation active products. As an example of the last named auxiliaryproducts may be cited the acetate of oleyldiethylamino-ethylamide aswell as the heptadecyi N-methyl-N'-ethylbenzimidazolium chloride. Thesesolutions, whether they contain additional materials or not, have theproperty that when they are heated or treated with alkaiies theydecompose, insoluble bodies being precipitated. When this happens on asubstratum, for instance a textile, this insoluble body is precipitatedin an adherent form. It may, according to its nature, impart to thefiber valuable properties. As further characteristics which may beimparted to the fiber there may be named the stability to creasing andto shifting of the warp and weft, the diminution of lustre, the increaseof resistance to water, the prevention of shrinkage in the fabric and inthe case of wool the prevention of felting.

By a suitable choice of the parent material the products of theinvention may be useful as wetting, emulsifying, foam-producing.levelling, softening agents and as agents enhancing the fastness ofdyeings to water, also as disinfectants or preservatives. For thesepurposes products are especially suitable which contain an aliphaticradical having about 12 carbon atoms.

The products of the invention may be used alone or, as already stated,in conjunction with other substances. Apart from the above-namedauxiliaries (thioureas, ureas, capillary active cation products) theremay be used for example salts, especially those of weak acids, forexample sodium acetate, ammonium acetate, aluminium formate, aluminiumacetate, ammonium sulfocy- 4 snide, also solvents. hydrocarbons such asparaffin, wax, soaps, soap-like substances. protective colloids,dressing agents, loading materials, softening agents. matting agents orthe like.

The following examples illustrate the invention, the parts belnl byweight:

Example 1 remains in the form of a semi-solid mass which decomposes whenboiled in aqueous solution or on addition of alkalies with the formationof a compound insoluble in water.

trample 2 Into 600 parts by volume of absolute alcohol are introducedsuccessively while stirring at 40- 50 0., 200 parts of methylolbenzamide, 105 parts of thiourea and a concentrated solution of 00 partsof HCl in absolute alcohol. The solution which very soon becomes clearis stirred for 1% hours at 40-50 0., then overnight at room temperature,and finally for 2 hours while cooling with ice. After filtering and(1171118. the new condensation product is obtained in the form of acolorless crystalline powder, having probably the formula HCI Example 32.3 parts of lauric acid methylolamide are disf solved in 25 parts byvolume of hot alcohol and C after cooling to 50 C. and while stirring, 4parts of finely powdered N-phenylthiourea are added,

followed by 2 parts by volume of alcoholic hydrochloric acid of 20 percent. strength. After stirring for 10-15 minutes at 40-50 C. a sample issoluble in water. The clear solution is evaporated at 40-50 C. in avacuum and the condensation product having probably the formula O C H|[CBali-0 NH is left in the form of a mass resembling wax.

This application is a division of our application Serial No.v 251,850,filed January 19, 1939 (now Patent No. 2,331,387, issued October 12,1943).

What we claim is:

1. Process for the manufacture of condensation products, which comprisescondensing a thiourea compound of the formula N-Ri wherein R1, R1 and Baare members or the group 30 consisting of hydrogen, aikyl, and andaraikyi radicals, with a methylol compound 0! an aliphatic primaryamide, the said methyloi compound containing at the most 13 carbon atomsat least '7 of which are connected, in the presence of acids anddiluents.

3. Process for the manufacture oi condensation products, which comprisescondensing thiourea with the methylol amide or the formula 0CHz-(CHQnr-("J-NH-ClEb-OH in the presence oi acids and diluents.

4. Process for the manufacture or condensation products, which comprisescondensing N- phenyl-thiourea with the methyloi amide or the formula inthe presence of acids and diluents.

5. Process for the manufacture of condensation products, which comprisescondensing thiourea with the methylol amide or the formula 0G-E-NH-CHl-OH in the presence of acids and diiuents.

CHARLES GRAENACHER. RICHARD SALLMAN.

Certificate of Correction Patent No. 2,411,655.

November 26, 1946.

CHARLES GRAENACHER ET AL.

It is hereby certified that errors appear in the printed specificationof the above numbered patent requiring correction as follows: Column 1,line 21, after potassium strike out the comma; column 2, line 14, afteriauric" insert a comma; and that the said Letters Patent should be readwith these corrections therein that the same may conform to the recordof the case in the Patent Office.

Signed and sealed this 25th day of February, A. D. 1947.

LESLIE FRAZER,

First Assistant Commissioner of Patents.

This application is a division of our application Serial No.v 251,850,filed January 19, 1939 (now Patent No. 2,331,387, issued October 12,1943).

What we claim is:

1. Process for the manufacture of condensation products, which comprisescondensing a thiourea compound of the formula N-Ri wherein R1, R1 and Baare members or the group 30 consisting of hydrogen, aikyl, and andaraikyi radicals, with a methylol compound 0! an aliphatic primaryamide, the said methyloi compound containing at the most 13 carbon atomsat least '7 of which are connected, in the presence of acids anddiluents.

3. Process for the manufacture oi condensation products, which comprisescondensing thiourea with the methylol amide or the formula 0CHz-(CHQnr-("J-NH-ClEb-OH in the presence oi acids and diluents.

4. Process for the manufacture or condensation products, which comprisescondensing N- phenyl-thiourea with the methyloi amide or the formula inthe presence of acids and diluents.

5. Process for the manufacture of condensation products, which comprisescondensing thiourea with the methylol amide or the formula 0G-E-NH-CHl-OH in the presence of acids and diiuents.

CHARLES GRAENACHER. RICHARD SALLMAN.

Certificate of Correction Patent No. 2,411,655.

November 26, 1946.

CHARLES GRAENACHER ET AL.

It is hereby certified that errors appear in the printed specificationof the above numbered patent requiring correction as follows: Column 1,line 21, after potassium strike out the comma; column 2, line 14, afteriauric" insert a comma; and that the said Letters Patent should be readwith these corrections therein that the same may conform to the recordof the case in the Patent Office.

Signed and sealed this 25th day of February, A. D. 1947.

LESLIE FRAZER,

First Assistant Commissioner of Patents.

